J-aggregate Films Research Articles

Analyte-dependent Rabi splitting in solid-state plexcitonic sensors based on plasmonic nanoislands strongly coupled to J-aggregates

A key challenge in the field of plexcitonic quantum devices is the fabrication of solid-state, device-friendly plexcitonic nanostructures using inexpensive and scalable techniques. Lithography-free, bottom-up nanofabrication methods have remained relatively unexplored within the context of plexcitonic coupling. In this work, a plexcitonic system consisting of thermally dewetted plasmonic gold nanoislands (AuNI) coated with a thin film of J-aggregates was investigated. Control over nanoisland size and morphology allowed for a range of plasmon resonances with variable detuning from the exciton. The extinction spectra of the hybrid AuNI/J-aggregate films display clear splitting into upper and lower hybrid resonances, while the dispersion curve shows anti-crossing behavior with an estimated Rabi splitting of 180 eV at zero detuning. As a proof of concept for quantum sensing, the AuNI/J-aggregate hybrid was demonstrated to behave as a plexcitonic sensor for hydrochloric acid vapor analyte. This work highlights the possibility of using thermally dewetted nanoparticles as a platform for high-quality, tunable, cost-effective, and scalable plexcitonic nanostructures for sensing devices and beyond.

Enhancing cooperativity of molecular J-aggregates by resonantly coupled dielectric metasurfaces

Abstract J-aggregates are supramolecular assemblies of dyes exhibiting strong absorption and fluorescence with narrow linewidths, as well as large optical nonlinearities, induced by the formation of largely delocalized molecular excitons. The degree of cooperativity achievable in J-aggregates ensembles, however, is limited by local disorder and thermally induced decoherence effects. A way to overcome these limitations and increase molecular exciton delocalization and coherence is to couple the ensemble of highly ordered molecular dipoles to a common electromagnetic mode in an optical resonator. In this work, we use dielectric metasurfaces to alter the radiative properties of coupled J-aggregate films and demonstrate a 5-fold Purcell enhancement of the luminesce intensity and narrowing of the emission directivity down to ∼300 mrad around the normal. These results highlight the potential of designer dielectric metasurfaces to foster the emergence of cooperative phenomena in excitonic systems, including optical nonlinearities and superradiance.

Strong Coupling of Chiral Frenkel Exciton for Intense, Bisignate Circularly Polarized Luminescence.

We show that chiral Frenkel excitons yield intense circularly polarized luminescence with an intrinsic dissymmetry factor in emission glum as high as 0.08. This outstanding value is measured through thin films of cyanine J-aggregates that form twisted bundles. Our measurements, obtained by a Mueller polarization analysis, are artifact-free and reveal a quasi-perfect correlation between the dissymmetry factors in absorption, gabs , and in emission glum . We interpret the bisignate dissymmetry factors as the signature of a strong coupling between chiral Frenkel excitons longitudinally excited along the bundles. We further resolve by polarimetry analysis the split in energy between the excited states with a Davydov splitting as small as 28 meV. We finally show the anti-Kasha nature of the chiral emission bands with opposite optical chirality. These mirror-imaged emissive chiroptical features emerge from the structural rigidity of the bundles that preserves the ground- and excited-state chirality.

Development of a highly efficient, strongly coupled organic light-emitting diode based on intracavity pumping architecture.

We report a highly efficient polariton organic light-emitting diode (POLED) based on an intracavity pumping architecture, where an absorbing J-aggregate dye film is used to generate polariton modes and a red fluorescent OLED is used for radiative pumping of emission from the lower polariton (LP) branch. To realize the device with large-area uniformity and adjustable coupling strength, we develop a spin-coating method to achieve high-quality J-aggregate thin films with controlled thickness and absorption. From systematic studies of the devices with different J-aggregate film thicknesses and OLED injection layers, we show that the J-aggregate film and the pump OLED play separate roles in determining the coupling strength and electroluminescence efficiency, and can be simultaneously optimized under a cavity design with a good LP-OLED emission overlap for effective radiative pumping. By increasing the absorption with thick J-aggregate film and improving the electron injection of pump OLED with Li2CO3 interlayer, we demonstrate the POLED with a large Rabi splitting energy of 192 meV and a maximum external quantum efficiency of 1.2%, a record efficiency of POLEDs reported so far. This POLED architecture can be generally applied for exploration of various organic materials to realize novel polariton devices and electrically pumped lasers.

Observation of Strong J-Aggregate Light Emission in Monolayer Molecular Crystal on Hexagonal Boron Nitride.

J-aggregates are widely used in studies of light-matter interaction and organic optoelectronic devices. Although J-aggregate films can be fabricated on salt by epitaxial growth method, the size is limited to hundreds of nanometer. In this work, with hexagonal boron nitride (h-BN) as a substrate, highly crystalline J-aggregate ultrathin films of N,N'-ditridecylperylene 3,4,9,10-tetracarboxylic diimide (PTCDI-C13) are achieved by physical vapor transport (PVT) method. Significant bathochromically shifted absorption band and narrowed 0-0 transition are observed in the monolayer PTCDI-C13 crystal on h-BN. The exciton coherence number Ncoh of monolayer J-aggregate film extracted from the photoluminescence (PL) spectrum is up to 15 at T = 140 K, which is higher than that of the epitaxially grown layer on salt. Beyond the first molecular layer, the multilayer crystal on h-BN is dominated by H-aggregates. Further study shows that that the first molecular layer on h-BN adopts the highly ordered face-on configuration, while the overlayers adopt the edge-on motif. As a comparison, only H-aggregate PTCDI-C13 ultrathin films are found on SiO2 substrates, but no J-aggregates. The results suggest that high-quality J-aggregates can be prepared by utilizing appropriate substrates via physical vapor transport.

Fabrication of Dipole-Aligned Thin Films of Porphyrin J-Aggregates over Large Surfaces.

We report a new approach for large-scale alignment of micron-sized J-aggregates of a derivative of porphyrin onto planar glass substrates. We applied a unidirectional nitrogen flow to an aqueous dye drop deposited onto a glass substrate to form an about 5 nm thick film of aligned J-aggregates over macroscopic surface areas up to several millimeters. The inter-aggregate distance is ∼500 nm, and it scales with the nitrogen pressure. We verified the film thickness and J-aggregate alignment using multimodal microscopy and spectroscopy techniques. Our technique is fast, simple, and cost-effective for producing large two-dimensional (2-D) arrays of aligned emitters.

Surface Exciton Polaritons: A Promising Mechanism for Refractive-Index Sensing

The possibility of constructing a surface exciton polariton (SEP) based sensor at room temperature is explored. The proposed SEP sensor is based on the Kretschmann-Raether configuration of conventional surface plasmon resonance (SPR) sensor, where the metal thin film was replaced by the J-aggregate cyanine dye film. The excitation of SEP results in a strong electric field at the interface of TDBC and analyte, and exponentially decaying into the analyte, which is sensitive to the refractive index variations of analyte. The sensitivity of 118.1818 $^\circ/\text{RIU}$ (140.4286 $^\circ/\text{RIU}$) was achieved for the proposed SEP sensor within the refractive index range 1.0-1.001 (1.33-1.36) of gaseous analyte (aqueous solutions), which is about 2 (3.5) times higher than that of conventional gold-based SPR sensor. The significant superiority of the SEP sensor in sensitivity revealing SEP as a new promising mechanism for sensing applications.

Femtosecond laser irradiation of molecular excitonic films for nanophotonic response control and large-area patterning.

Molecular excitonic films such as J-aggregate thin films can show an optically metallic response in the visible region and can be considered as alternative materials for plasmonics. However, there was no direct, top-down method to modify the optical response over a large area. Here, we demonstrate the femtosecond (fs) laser processing of J-aggregate films on the centimeter scale. With proper laser conditions, optically metallic films (Re[ε] < 0) were modified to dielectric ones (Re[ε] > 0) with large changes in optical responses. We performed various optical spectrum measurements to investigate the effect of fs-laser irradiation. Our results demonstrate that the strong modification of the optical response can be induced over a large area by fs-laser processing and this can be useful for novel nanophotonic studies.

Angle-dependent optical perfect absorption and enhanced photoluminescence in excitonic thin films

We experimentally demonstrate perfect absorption of incident light in an ultrathin, planar organic layer, together with large photoluminescence (PL) enhancement. We find that diverse features appear in the absorption spectra of J-aggregate excitonic films, depending on the incident light angle and the phase controller thickness. We achieve strong absorption even away from the excitonic absorption pole. We explain the angle-dependent perfect absorption by comparing radiative and nonradiative damping rates for different incident angles. Moreover, we achieve large PL enhancement at strong light absorption conditions. This demonstrates that the absorbed light energy in excitonic perfect absorbers can be retrieved, unlike other perfect absorbers based on metal nanostructures where the absorbed energy is mainly dissipated as heat due to ohmic losses. Excitonic perfect absorbers can be useful for energy conversion devices or fluorescence-based optical devices.

How two-dimensional brick layer J-aggregates differ from linear ones: Excitonic properties and line broadening mechanisms.

We study the excitonic coupling and homogeneous spectral line width of brick layer J-aggregate films. We begin by analysing the structural information revealed by the two-exciton states probed in two-dimensional spectra. Our first main result is that the relation between the excitonic couplings and the spectral shift in a two-dimensional structure is different (larger shift for the same nearest neighbour coupling) from that in a one-dimensional structure, which leads to an estimation of dipolar coupling in two-dimensional lattices. We next investigate the mechanisms of homogeneous broadening--population relaxation and pure dephasing--and evaluate their relative importance in linear and two-dimensional aggregates. Our second main result is that pure dephasing dominates the line width in two-dimensional systems up to a crossover temperature, which explains the linear temperature dependence of the homogeneous line width. This is directly related to the decreased density of states at the band edge when compared with linear aggregates, thus reducing the contribution of population relaxation to dephasing. Pump-probe experiments are suggested to directly measure the lifetime of the bright state and can therefore support the proposed model.

Photodetectors based on single-walled carbon nanotubes and thiamonomethinecyanine J-aggregates on flexible substrates

The present paper is devoted to observations of the photoresistive effect in multilayer structures with a sensitive layer of J-aggregates of thiamonomethinecyanine polymethine dye and a transparent electrode of a conductive carbon-nanotube network on a flexible polyethylenenaphtalate substrate. The effect of narrow-band emission with a wavelength of 465 nm on a change in the conductivity of the fabricated structures is studied. The prepared samples are studied by atomic-force microscopy, Raman spectroscopy, and spectrophotometry methods. It is shown that these structures are photosensitive to the indicated spectral region, and the dye layer is a film of dye J-aggregates. The change in the sample conductivity upon exposure to light one hundred times exceeds the dark conductivity. In general, the principal possibility of developing a photoresistive detector based on J-aggregates of cyanine dyes on flexible supports on account of the use of transparent and conductive carbon-nanotube layers is shown.

Temperature and concentration dependence of J-aggregate of a cyanine dye in a Laponite film fabricated by Langmuir–Blodgett technique

In this communication, we report the temperature and concentration dependence of J-aggregate of a cyanine dye N,N′-dioctadecylthiacyanine perchlorate (NK) in the Laponite film fabricated by Langmuir–Blodgett technique. Surface pressure area per molecule isotherm revealed the formation of stable Langmuir monolayer at the air–water interface. Spectroscopic characterization confirmed the formation of J-aggregates in the NK LB film without Laponite. In the hybrid film, J-aggregate forms at lower Laponite concentration (1ppm), higher deposited surface pressure and at lower subphase temperature. Both the J-aggregated films were found to be optical second harmonic generation (SHG) active and mechanically very stable, although intrinsically NK is SHG inactive.

Process dependence of morphology and microstructure of cyanine dye J-aggregate film: correlation with absorption, photo- and electroluminescence properties.

Cyanine dye J-aggregate films are a class of absorbing and luminescent materials which have been extensively applied in the polariton-based research. Here we systematically study the DEDOC cyanine dyes J-aggregate films made by layer-by-layer assembly and spin-coating processes to establish a clear correlation between the film structure and the absorption and luminescence properties. From detailed analyses of morphology, optical spectra, and light-emitting diode characteristics, we demonstrate that layer-by-layer assembled film has higher degrees of homogeneity and molecular packing quality than spin-coated film, leading to a higher absorption coefficient, more uniform luminescence, and a greater electroluminescence quantum efficiency with maximized thickness.

Fractal structures in n-phenyl-porphyrin J-aggregate films

Studied here are thin films of a series of phenyl-porphyrins. The effect of the phenyl number and positioning on the porphyrin core is shown to have a significant impact on the ability of phenyl-porphyrins to produce aggregates. When four phenyl groups (H2TPP) and three phenyl groups are present (H2-Tri-PP) a strong aggregate film forms with fractal like structure. When two phenyl groups are present little evidence for aggregation can be determined, however fractal structure persists.

Anisotropic Optical Properties of Thin-Film Thiacarbocyanine Dye Aggregates

Optical properties of thin films of aggregated thiacarbocyanine (TCC) dyes have been studied by means of spectroscopic ellipsometry and polarized IR spectroscopy. The experimental results reveal a strongly anisotropic response of the films, as quantified in the reported anisotropic dielectric functions over a wide range of frequencies. The studied TCC films exhibit both J-aggregate and H-aggregate absorption bands with different polarization properties. A strong dielectric resonance arising from the J-aggregate electronic excitations was found to be polarized along the film. The observations are consistent with the preferential orientation of aggregate filaments along the films. We have also used the measured anisotropic properties in model calculations of energy transfer into thin films of J-aggregates to illustrate the potential importance of accurate optical characterization in engineering aggregate-based hybrid nanostructures for optoelectronic applications.

Exciton transport and electron mobility of organized aggregates of cationic dye thiocyanates

Films of cationic dye thiocyanates adsorbed on copper based substrates form organized structures by a process of templated self-assembly. The growth process is initiated by strong S-bonding of thiocyanate ions to Cu sites, followed by repetitive and alternate bonding of dye cations and thiocyanate anions by electrostatic and dipolar forces. Rhodamine B thiocyanate and several other cationic dye thiocyanates solid films deposited this way exhibit J-aggregation behavior with large red-shifts in the absorption spectrum. Photoelectrochemical experiments with Rhodamine B thiocyanate deposited CuSCN cathodes indicated exciton diffusion lengths of order of 100 nm and space charge saturation current measurements suggested nearly three orders of magnitude enhancement of the electron mobility in the J-aggregated film. The photovoltaic properties of heterojunctions sandwiching J-aggregated dye films between n- and p-type semiconductor surfaces are investigated for potential application as solar cells and photon detectors.

Twenty-Fold Enhancement of Molecular Fluorescence by Coupling to a J-Aggregate Critically Coupled Resonator

We report a 20-fold enhancement in the fluorescence of the organic dye DCM when resonantly coupled to a strongly optically absorbing structure of a thin film of spin-deposited molecular J-aggregates in a critically coupled resonator (JCCR) geometry. A submonolayer equivalent of DCM molecules is shown to absorb and re-emit 2.2% of the incident resonant photons when coupled to the JCCR enhancement structure, compared to 0.1% for the bare film of same thickness on quartz. Such a JCCR structure is a general energy focusing platform that localizes over 90% of incident light energy within a 15 nm thin film layer in the form of excitons that can subsequently be transferred to colocated lumophores. Applications of the exciton-mediated concentration of optical energy are discussed in the context of solid-state lighting, photodetection, and single photon optics.

Suppression Mechanism of the Photodegradation of J-Aggregate Thin Films of Cyanine Dyes by Coating with Polysilanes

To clarify the suppression mechanism of the photodegradation of J-aggregate thin films of cyanine dyes induced on the coating with polysilanes, we have studied photochemical and electrochemical properties of composite films of J-aggregate of cyanine dyes and polysilanes. We have determined onset oxidation potentials of both J-aggregate thin films and polysilane thin films by employing an ITO electrode slab-optical waveguide spectroscopic system combined with an electrochemical measurement system. It has been clarified that photodegradation efficiency decreases with an increase in the onset oxidation potential of J-aggregate, indicating that the photodegradation of J-aggregate thin film mainly proceeds via its radical cation produced from the first excited singlet state, and polysilanes donate an electron to the radical cation to suppress the photodegradation. Film thickness and molecular orientation of polysilane were found to be important factors to suppress the photodegradation.

Effects of alkoxy substitution on the crystal structure of 2,3-bis[(E)-4-(diethylamino)-2-alkoxybenzylideneamino]fumaronitrile derivatives

The bisazomethine dyes derived from diaminomaleonitrile and aminobenzaldehydes, 2,3-bis[(E)-4-(dialkylamino)benzylideneamino]fumaronitrile derivatives, are known to have potential as dyes for forming J-aggregate vapour-deposited films, even though appropriate conditions for preparation of their pure J-aggregate films are unknown. In this study, an attempt was made to investigate the effects of alkoxy substitution on the crystal structures of eight bisazomethine dyes; our final goal was to obtain pure J-aggregates of bisazomethine dyes in a crystalline state. The focus of this study is on the relationship between changes in the molecular structure and the crystal structure, characterized by a two-dimensional molecular stacking layer and its alignment. We found that the interlayer distance between adjacent two-dimensional stacking layers can be controlled by alkoxy substitution, when the substituent chain length is less than C10, without any significant structural changes in the stacking layer. Our observation was confirmed by lattice energy calculations from an energetic perspective.

Exciton-exciton annihilation in organic polariton microcavities

We investigate the incoherent diffusion of excitons in thin films ($5.1\ifmmode\pm\else\textpm\fi{}0.1\text{ }\text{nm}$ thick) of a highly absorbing J-aggregated cyanine dye material (${10}^{6}\text{ }{\text{cm}}^{\ensuremath{-}1}$ absorption constant) as the excitonic component of a polariton microcavity. Under high-intensity pulsed laser excitation, the J-aggregated molecular films exhibit significant exciton-exciton annihilation, indicating a large exciton diffusion radius of more than 100 nm. When the material is strongly coupled to a cavity, the polaritonic structure also shows exciton-exciton annihilation, which is a competing process against the establishment of a threshold population of polaritons needed for polariton lasing. This study suggests that exciton-exciton annihilation is a loss process which can significantly increase the lasing threshold in polariton microcavities.